Three synthetic routes to the unusual supramolecular complex ([Cp2Co]2[{(OC)5V}2(μ-1,4-CNC6Me4NC)])∞, which was crystallographically characterized, are presented. The dianion [{(OC)5V}2(μ-1,4-CNC6Me4NC)]2− constitutes the first subvalent organometallics featuring a diisocyanoarene linker.